Urea resin curing agents, compositions, and process for the improvement in the properties of textiles



United States Patent 9 f 3,060,061 UREA RESIN CURING AGENTS,COMPOSITIONS,

AND PROCESS FOR THE IMPROVEMENT IN THE PROPERTIES OF TEXTILES PeterLoebler, Troisdorf, Robert Helligrath, Dusseldorf,

Horst Eisner, Spich, and Richard Huttenlocher, Lendersdorf, uher Duren,Germany, assignors to Chemische Fabrik Diiren G.m.b.H., Duren,Rhineland, Germany, a corporation of Germany No Drawing. Filed Nov. 14,1960, Ser. No. 69,228

- Claims priority, application Germany Nov. 12, 1959 24 Claims. (Cl.117-1394) The present invention relates to curing agents forureacontaining resin materials, resin compositions and processes forimproving the wearing properties of textiles and rendering such textilesresistant to tearing, creasing, washing action and attack by chlorine.

It is well known to improve the properties of textiles by impregnatingthe same with synthetic resin materials. It has always been consideredforemost in this connection to obtain high magnitude dry and wetcreasing angles with respect to cotton and Wool staple fibers, yarns,fabrics and the like, while at the same time not sacrificing as far aspossible the strength and resistance qualities of the particular staplefibers, yarns and fabrics. The properties of resistance to tearing andto the normal rubbing wear of the synthetic resin finished fabrics oughtnot to exhibit decreases in comparison to these properties in untreatedtextile materials. When employing synthetic resin finishes, obviouslythe utility value of the textile fabrics must be preserved.

The washing stability of such synthetic resin finishes with respect totextile fabrics, of course, is quite important and in this connectioncommercial requirements demand that such synthetic resin finishes beable to endure twenty or more washings at temperatures of from 80 to 90C. without marked loss of the desired textile properties.

In many instances, washing procedures contemplate treatment of cottonand wool staple fibers and/ or fabrics in the course of the washing withalkali hypochlorite solutions and preparations. Inasmuch as urea resinsand melamine resins as well as ethylene-urea resins which have not beencompletely condensed, are often used for impregnating textile materials,severe fabric damage may occur due to the fact that such resins stillcontain groups reactive with respect to chlorine. Chlorine is present inwashing solutions as a consequence of the use of alkali hypochloritesubstances, and therefore readily attacks the textiles by reacting withthe incompletely condensed resin impregnants. Consequently, at highironing temperatures the chlorine addition products of the syntheticresin impregnants decompose, whereupon the fabrics become discolored ordarkened, often turning brown, and the staple fiber material hydrolyzesand loses its strength and resistance characteristics.

In order to overcome such disadvantages in view of the increasedrequirements for impregnated textile materials, various hardeners havebeen suggested for thecondensation of urea-, melamine-,ethylene-urea-formaldehyde-precondensate used as textile impregnants. Itwas found that ammonium salts of inorganic and organic acids wereunserviceable where chlorine-resistant finishes were desired. Althoughsomewhat better, salts of organic bases with inorganic and organic acidswere also considered poor in performance with respect to stabilitytowards chlorine in the hardened or cured impregnant, and in most casessuch salts exhibited insufficient resistance to washing action. Zincsalt, calcium salt and particularly magnesium salt catalysts have provedto be good as curing agents for the hardening of urea resins. Magnesiumchloride is preferred in this respect since with magnesium chloride3,060,061 Patented Oct. 23., 1962 "ice catalysts, good stability tochlorine of the condensed resin impregnant is obtained. While theresistance to washing action is generally good, the aforementioned metalsalt catalysts unfortunately attack the cellulose staple fibers,

impair the strength and resistance properties, and damage the utilityeffectiveness of the fabrics. With regard to these properties, zinc,calcium and magnesium salts are similar in action to that of ammoniumsalts of inorganic acids, such as ammonium chloride, ammonium nitrateand ammonium phosphate, all leading to the formation with ureaprecondensates of hard, brittle synthetic resins which result inundesired fiber damage of the finished textile.

It is an object of the present invention to overcome the foregoingdrawbacks and to provide curing agents for urea-containing resinmaterials, resin compositions and processes for improving the wearingproperties of textiles and rendering such textiles resistant to tearing,creasing, Washing action and attack by chlorine.

Other and further objects of the invention will become apparent from astudy of the within specification and the accompanying examples.

In accordance with the present invention, it has been found that byusing salts of weak organic bases with semi-amides formed fromethylene-o /i-dicarboxylic acid and amines, as curing agents orhardening components for effecting the curing or hardening of urea resincondensates, the properties of textile fabrics, yarns, fibers and thelike are substantially improved. The curing agents or hardeningcomponents in accordance with the invention produce with urea resinssofter end-condensates than could be achieved heretofore. Textilematerials impregnated with urea resin precondensates which are heathardened in the presence of the salts of Weak organic bases withsemiamides in accordance with the process of the invention, possessextraordinary resistance properties with respect to tearing, creasing,washing action, attack by chlorineand, in spite of slight embrittling ofthe fibers, excellent wet and dry creasing angles.

The effect of curing agents or hardening components in accordance withthe invention is particularly noteworthy when they are used inquantities of from about 10- 20% by Weight based upon the initial chargeof synthetic resin precondensate. Thus, all urea-, melamine-,ethyleneurea-formaldehyde-precondensates may be heat hardened atelevated temperatures, for example, at C., in accordance with theinvention to form final condensed resins having the desired properties.Conveniently in accordance with the invention the textile material maybe impregnated with the precondensate containing the curing or hardeningcomponent and thereafter subjected to conventional heat hardening withthe application of normal procedures, including imprint calendering atelevated temperatures to achieve the usual desired printing effects.

Weak organic bases which may be used to form the curing component saltsin accordance with the invention include aliphatic and aromatic amines,and in particular dicyanide diamide, melamine, triazine, imidazoles,pyrroles, pyridines and the like. The semi-amides may include anyethylene-a,{3-dicarboxylic acid such as substituted and unsubstitutedmaleic acid, with an aliphatic amine or cyclic amine polyamine such asmorpholine, N-cyclohexylamine, N-alkoxy amines such as N-fi-ethoxyamine, and generally any primary, secondary or tertiary amine. Thus, anyN-su-bstituted ethylene-u,B-dicarboxylic acid semi-amide may be usedwith the weak organic base to form the desired salt.

In accordance with the invention, the curing component may comprise thefollowing salts: maleamic acid melamine salt; N-B-ethoxy maleamic acidmelamine salt; melamido-maleamic acid melamine salt; the melamine saltof 1,2-bis(maleamic acid)ethylene; N-cyclohexyl malearnic' acidmelaminesalt; semi-substituted morpholino maleic acid-melamine salt, andthe like.

The end-condensates or finished or hardened resins obtained inaccordance with the invention exhibit only very slight or no-chlorinebinding capacity, which proves that allreactive groups in the hardenedsynthetic resins are blocked and that practically a quantitativecondensation has-been attained. By means of the curing salts of theinvention, modern day requirements are satisfactorily fulfilled withrespect to urea resin finishes on cellulose fibers. Textile materialsimpregnated with urea-containing hardenable resins having incorporatedtherein the salts of the present invention possess high crease-freeproperties and extensive fiber protection and resistance to tearing andwashing action. The stability of the finished resin-impregnated textilewith respect to chlorine, as for example may be present in a chlorinecleaning solution, is excel lent. Moreover, in most cases it has beenfound unnecessary to after-treat the finished fabrics by Washing sincethe finished condensed impregnants are neutral in effect. In contrastthereto, where metal salt catalysts, such as zinc, calcium and magnesiumsalts, are used in effecting the hardening of the impregnants ontextiles, subsequent Washing must be carried out to render the finishedtextiles commercially acceptable.

The following examples are set forth for the purpose of illustrating theinvention, and it is to be understood that the invention is not to belimited thereto.

Example 1 An impregnating solution for the finishing of cotton printgoods contains 80 grams of dimethylol-urea per liter of liquor as resin,and the solution is separately treated with the various catalystsindicated below. After impregnating the cotton print goods on a pad inthe usual manner using a different catalyst (a to e) in each instance,the fabric is preliminarily dried in the normal way and subsequentlyafter-condensed for 3 minutes at 160 C. Separate samples of theimpregnated cotton print goods (each sample. containing a differentcatalyst, a to e), are thereafter subjected to washing action for 15minutes in a boiling solution of 2 grams of soap and 3 grams of soda.The results obtained are set forth below:

Synthetic resin loss after boiling-washing for 15 minutes with 2 g. soapand 3 g. soda, percent by Catalyst weight (a) 4 g. ammoninmchloride- 33(b) 4 g. ammonium phosphate 41 (c) 5 g. monoethanolamine phospha 45 (d).7 1;. magnesium chloride 51 (c), 8 g. maleamic acid melamine salt 18Example 2 Poplinshirt material is finished with 80 g. ofdimethylolethylene-urea per liter of liquor as resin in the same manneras carried out in Example 1. The poplin fabric is treated in the usual.way with the synthetic resin precondcnsate solution on a pad, thereafterpreliminarily dried and then condensed for 3 minutes at 160 C. Thefollowing results are obtained:

4.- Example 3 A wool staple fiber fabric is impregnated on a pad in theusual manner with grams of a dimethylol compound of ethylene-urea and 20grams of the dimethylol compound of diethylene-triurea, per liter ofliquor, in the presence of thevarious catalysts setzforth below, in thesame way as carried out in accordance with Example 1. The resin materialimpregnated textile is then carefully pre-dried such that the fabricstill contains 10% residual moisture. The fabric is then imprinted on animprint calender undera pressureof-S to 6 lcg./cm. and at a rollertemperature of 190 C.,.and subsequently. condensed for 3 minutes at C.

' Synthetic resin loss after boiling-washing for 15 minutes with 2 g.soap and 3 g. soda, percent by Catalyst What is claimed is:

1. In the process for improving the properties of textile materialsincluding fabrics, yarns, fibers, and the like by treatment withurea-containing hardenable resins selected from the group consisting ofurea-, melamineand ethylene-urea-formaldehyde-precondensates, theimprovement which comprises effecting the hardening of theureacontaining hardenable resin material by heating with a salt of aweak organic base with a semi-amide formed from anethylene-a,fi-dicarboxylic acid and an amine.

2. Improvement according to claim 1 wherein the weak organic base ismelamine.

3. Improvement according to claim 1 wherein. the amine used to form thesemi-amide is selected from the group consisting of aliphatic amines andcyclic amines.

4. Improvement according to claim 1 wherein the semiamide is anN-substituted ethylene-a48-dicarboxylic acid semi-amide.

5. Improvement according to claim 1 wherein the salt is maleamic acidmelamine salt.

6. Improvement according to claim 1 wherein the salt is N-fl-ethoxymaleamic acid melamine salt.

7. Improvement according to claim 1 wherein the salt ismelamido-maleamic acid melamine salt.

8. Improvement according to claim 1 wherein the salt is the melaminesalt of 1,2-bis(maleamic acid)-ethylene.

9. Improvement according to claim 1 wherein the salt is N-cyclohexylmaleamic acid melamine salt.

10. Improvement according to claim 1 wherein the salt issemi-substituted morpholino maleic acid melamine salt.

11. Improvement according to claim 1 wherein the salt is used in anamount of from about 1020% by weight of the urea-containing hardenableresin material under the application of heat.

12. Process for curing urea-containing hardenable resin materialselected from the group consisting of urea-, melamineandethylene-urea-formaldehyde-precondensates which comprises effecting thecuring by heating in the presence of a salt of a weak organic base witha semiamide formed from an ethylene-a,fl-dicarboxylic acid and an amine.

13. Hardened urea-containing resin on a substrate produced by heating onthe substrate a hardenable urea-containing resin precondensate selectedfrom the group consisting of urea-, melamineandethylene-urea-formaldehyde-precondensates with a salt of a weak organicbase with a semi-amide formed from an ethylene-medicarboxylic acid andan amine in an amount of from about 1020% by weight of theprecondcnsate.

14. Textile material having impregnated therein a hardenedurea-containing resin resistant to tearing, creasing, washing action andattack by chlorine, produced by heat hardening a hardenableurea-containing resin precondensate selected from the group consistingof urea-, melamineand ethylene-urea-formaldehyde-precondensatesimpregnated in the textile material, with a salt of a weak organic basewith a semi-amide formed from an ethylene-a,5-dicarboxylic acid and anamine in an amount of from about -20% by weight of the precondensate.

15. Hardened urea-containing resin composition containing a heathardened member selected from the group consisting of urea-, melamineandethylene-urea-formaldehyde-precondensates, impregnated on a substrateand having incorporated therein a salt of a weak organic base with asemi-amide formed from an ethyleneedicarboxylic acid and an amine, in anamount of from about 10-20% by weight of the resin precondensate.

16. Composition according to claim wherein the weak organic base ismelamine.

17. Composition according to claim 15 wherein the amine used to form thesemi-amide is selected from the group consisting of aliphatic amines andcyclic amines.

18. Composition according to claim 15 wherein the semi-amide is anN-substituted ethylene-afi-dicarboxylic acid semi-amide.

19. Hardened urea-containing resin composition containing a heathardened member selected from the group consisting of urea-, melamineandethylene-urea-formaldehyde-precondensates, impregnated on a substrateand having incorporated therein maleamic acid melamine salt, in anamount of from about 10-20% by weight of the resin precondensate.

20. Hardened urea-containing resin composition containing a heathardened member selected from the group consisting of urea-, melamineandethylene-urea-formaldehyde-precondensates, impregnated on a substrateand having incorporated therein N-B-ethoxy maleamic acid melamine salt,in an amount of from about 10-20% by weight of the resin precondensate.

21. Hardened urea-containing resin composition containing a heathardened member selected from the group consisting of urea-, melamineandethylene-urea-formaldehyde-precondensates, impregnated on a substrateand having incorporated therein melamido-maleamic acid melamine salt, inan amount of from about 10-20% by weight of the resin precondensate.

22. Hardened urea-containing resin composition containing a heathardened member selected from the group consisting of urea-, melamineandethylene-urea-formaldehyde-precondensates, impregnated on a substrateand having incorporated therein the melamine salt of 1,2-bis- (maleamicacid)-ethylene, in an amount of from about 10-20% by weight of the resinprecondensate.

23. Hardened urea-containing resin composition containing a heathardened member selected from the group consisting of urea-, melamineandethylene-urea-formaldehyde-precondensates, impregnated on a substrateand having incorporated therein N-cyclohexyl maleamic acid melaminesalt, in an amount of from about 10-20% by weight of the resinprecondensate.

24. Hardened urea-containing resin composition containing a heathardened member selected from the group consisting of urea-, melamineandethylene-urea-formaldehyde-precondensates, impregnated on a substrateand havi-ng incorporated therein semi-substituted morpholino maleicacid, in an amount of from about 10-20% by weight of the resinprecondensate melamine salt.

References Cited in the file of this patent UNITED STATES PATENTS2,466,744 Scott Apr. 12, 1949

1. IN THE PROCESS FOR IMPROVING THE PROPERTIES OF TEXTILE MATERIALSINCLUDING FABRICS, YARNS, FIBERS AND THE LIKE BY TREATMENT WITHUREA-CONTAINING HARDENABLE RESINS SELECTED FROM THE GROUP CONSISTING OFUREA-, MELAMINE- AND ETHYLENE-UREA-FORMALDEHYDE-PRECONDESATES, THEIMPROVEMENT WHICH COMPRISES EFFECTING THE HARDENING OF THEUREACONTAINING HARDENABLE RESIN MATERIAL BY HEATING WITH A SALT OF AWEAK ORGANIC BASE WITH A SEMI-AMIDE FORMED FROM ANETHYLENE-A,B-DICARBOXYLIC ACID AND AN AMINE.